Document mpzaapKO165vp1nK4vR4YVj14
^Catherine E. Reed, Ph.D.
3M Environmental, Health and
900 Bush Avenue, Building 42-2E-26
r Staff Vice President
Safety Operations
PO Box 33331
St. Paul, MN 55133-3331
H a 6 . lZH-%
651 778 4331
Certified Mail
05 SEP-? H ff):
f i* *
August 26, 2005
"T fc p -0*705"-~CiO 3 7 ?
Document Processing Center (Mail Code 7407M)
Room 6428
Attention: TSCA 8(e) Coordinator Office of Pollution Prevention and Toxics
4j H p
U.S. Environmental Protection Agency
1201 Constitution Avenue, N. W. Washington, D. C. 20460
C ontali) N r
NO TSCA CBI
CBI
Re: TSCA Section 8(e) Supplemental Notice: Sulfonate-based and Carboxylic-based Fluorochemicals, Docket Nos[8EHQ-l 180-374J8EHO-0381-0394: 8EHO-0598-373
Dear Sir:
3M is submitting this notice to supplement its previous submissions on sulfonyl and carboxylic-based fluorochemicals.
3M has recently received the enclosed analytical report which presents data from 36 lots of commercially available normal pooled human serum that were:purchased by the 3M Environmental Laboratory and subsequently screened for endogenous fluorochemicals. Each sample was analyzed using a protein precipitation technique and screened for sixteen different fluorochemicals, including perfluorooctane sulfonate (PFOS) (CgFnSCV) and perfluorooctanoic acid (PFOA) (C7F15COOH), using liquid chromatography/tandem mass spectrometry (LC/MS/MS). Much of the data presented in the report was derived from extrapolated curves and should be considered as screening quality data only and not necessarily representative of the general population levels. Not all of the detected chemicals are or were produced by 3M. In addition, the levels of fluorochemicals reported are generally corroborative of previously reported values and/or do not represent "substantial risk" information
If you have any questions, please do not hesitate to contact Dale L. Bacon at (651) 778-4736.
89050000597
Katherine D. Reed, PhD Staff Vice President Environmental Technology and Safety Services
050000597
BEST COPY AVAILABLE
I
l0J *1133 SOM
ysj i'! id c l
\ 1333H
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
NO TSCA CBI
Analytical Report
Revised August 12, 2005
initial Quantitative Screening of Commercial Lots of Human Serum Obtained in 2004 for Endogenous Fluorochemicals Using Protein Precipitation and Liquid Chromatography/Tandem Mass Spectrometry
Laboratory Request Number: E05-0120
Testing Laboratory
3M Environmental Health and Safety Operations 3M Environmental Laboratory
3M Environmental Laboratory
Project Lead Mark E. Ellefson Building 2-3E-09
PO Box 3331 Saint Paul, MN 55133-3331
Phone: 651-778-5405
Testing Facility Management William K. Reagen, Ph.D. . Building 2-3E-09 PO Box 3331
Saint Paul, MN 55133-3331 Phone: 651-778-6565
Requestor
Dale Bacon Building 2-3E-09
PO Box 3331 Saint Paul, MN 55133-3331
Phone: 651-778-4736
X Page 1 o f 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
3M Environmental Laboratory
Analytical Report
Project Number: E05-0120
ti
Hie following analytical report presents data from commercially available normal pooled human serum that were purchased by the 3M Environmental Laboratory and subsequently screened for endogenous fluorochemicals.
Thirty-six separate lots of pooled normal human, serum were extracted using a protein precipitation technique and screened for sixteen different fluorochemicals using liquid chromatography/tandem mass spectrometry (LC/MS/MS). Serum samples were received from various suppliers between 9/9/04 and 12/2/04. Samples were analyzed between 02/03/05 and 02/09/05;
This range-finding study was designed to provide lower limits o f quantitation (LLOQs) of approximately 100 - 300 ppt. Upon review of the data, it was discovered that many of the target analytes were present .at concentrations much lower than the 100 - 300 ppt target level. As an interim solution and until a more definitive study can be completed, signal to noise ratios were evaluated and a limit o f detection (LQD) was defined for each analyte. As a result, calibration curves were extrapolated between the LLOQ and the newly defined LOD, allowing screening quality data to be determined for some analytes as low as 19.9 ppt. Therefore, it must be emphasized that much o f the data presented in this report was derived from extrapolated curves and should be considered as screening quality data only.
Sample results are summarized in Table 1. The average values reported represent samples in which there was detectable analyte. Sample values that were less than the limit of detection were not included in the average value calculations. Please refer to Section 5 for individual sample results.
Page 2 o f 18
3
Table 1. Summary of Perfluorinated Acid Results
3M ENVIRONMENTAL LABORATORY PROJECT NO.EQ5-0120
Mean
3.33 2.84 NR 0.954 4.61 1.25 NR2 0.623 <L0D
Median High Low
Standard Deviation
3.33 7.08 0.507 2.17
2.5 3.56 2.45 0.627
~nfF NR2 NR2 NR2
0.954 1.02 0.888 0.0933
4.59 23.0 0.477 3.64
1.09 2,63 0.337 0.571
NR NR2
NR2 NR2
0.660 0.842 0 .3 1 2 0.208
<L0D <LOD <LOD ND1
Number of Samples with Detectable Analyte
20/36
3/35
0/36
2/36 35/36 34/36
0/36
6/36
0/36
ND1= N ot Detected. This analyte was not detected in any o f the samples. NR2= N o t Reported. This analyte was detected in one o f the 36 samples but appears to be a contaminant or an anomaly; the sample~will be reanalyzed and the results w ill be reported in the definitive study;
Table 2. Summary of Other Perfluorinated and Highly PIuorinated Analyte Results
Mean
<LOD 0.0776 0.0348 3.27 16.3
Median
<LOD 0.0401 0.0339 3.27 16.9
High Low
<LOD 0.199 0.0706 5.80 32.8
<LD 0.0311 0.0210 0.780 2.71
Standard Deviation
ND1 0.0812 0.0122 1.52 6.71
Fraction of Samples with Detectable Analyte
0/36 4/36 23/36 36/36 36/36
N D 1= N ot Detected. This analyte,was not detected in any o f ;the samples.
<LOD <LOD <LOD <LOD ND1
0/36
0.0839 0.0819 0.155 0.0480 0.0257
36/36
Peaks were observed in the chromatograms corresponding to linear and branched isom ers for PFOS and PFOA. Relative branched and linear isom er ratios were determined for both analytes and are presented below (the human serum value represents an average of % branched isomers for all of the human serum samples that contained detectable levels of each analyte). The % branched isomer results for individual samples are presented in Table 12. In addition, well-characterized lots of PFOS (Lot 171) and PFOA (Lot 332) were analyzed together as a matrix spike (QC050203-004) in rabbit serum. Data from that analysis was evaluated for branched and linear isomer distribution and agrees well with previously obtained NMRdata.
Page 3 of 18
m ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 3. Summary of PFOA and PFOS Isomer Ratios
Human Serum, average
Matrix Spike (QC050203-004) TCR-123 (99030-030) PFOA Lt 332 (NMR cfiaracterized value)
TCR-696 PFOS Lot 171 (NMR characterized value)
;`PF0 %Brancberi'i PFQS %Branched
Isomer
Isomer v ;
!.. i !*vs8Sv.
6% 39%
23% 32%
22%
31%
ce S t a a i i p
Tabl 4. Reference Substances
's f i - v * ' - S l l W i
Acronym^:
S P W P i ,:: d;I:
4'
M ,41
s
l
l y
, i
uml *belr"
J
` :,! P u 'm y l
Additional
Heptafluorobutyric Acid
PFBA (C4 Acid) ;
Aldrich
TCR-757.
99.2%
0.995
Nonafluoropentanoic acid
NFPA (C5 Acid)
Aldrich
TCR-333 (00017-045) 96.5%
0.996
Perfluorohexanoic acid
PFHA (C6 Acid) Oakwood Products
TCR-673
97.7%
0.997
Tridecafluoroheptanoie abid TDHA (C7 Acid)
Aldrich
TCR-267
98.2%
' 0.997
Perfluorooctanoic acid
PFOA (C8 Acid)
3M
TCR-123 (99030-030) 95.0%
0.958
Heptadecafluorononanoic acid
C9 Acid
Oakwood Products
TCR-618
,98.0%
, 0.998
Nonadecafluorodecanoic acid
CIO Acid
Oakwood Products
TCR-36
98.01%
0.998
Perfluoroundecanoic acid
C l 1 Acid
Oakwood Products
TCR-619
96.4%
0.998
Perfluorododecanoic acid
C l 2 Acid
Oakwood Products
TCR-37 (SD037) , , 99.65%
. 0.998
Perfluorobutanesulfonamide
. FBSA
3M ' TCR-314 (00017-2S) unknown
0.997
Perfluorooctanesulfonamide
FOSA
3M
TCR-280 (99131-038) 98.94%
0.997
Perfluorobutane sulfonate
PFBS
3M
TCR-282 (99131-040) 97.3%
0.885
Perfluorohexane sulfonate
PFHS
3M
TCR-83 (SE036)
98.6%
0.911
Perfluorooctane sulfonate
1H, 1H.2H.2H, perfluorooctanesulfonic acid
1H, 1H, 2H, 2H, perfluorodecane sulfonate
Perfluorooctanoic acid, isotopically labeled
| '
PFOS IHPFOS THPFDS i3r pp/-,*
3M SynQuest Labs
Pace/3M Perkin Elmer
TCR-696 TCR-343 (00017-055)
TCR-627 TCR-744
86.4% 93.5% 94.7% >97%
0.927 0.998 0.998 0.998
Page 4 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E0S-0120
The samples for this study were prepared as follows:
1. The serum samples were allowed to thaw and warm to room temperature.
2. One milliliter of serum (or water in the case o f method blanks) was added to a 15 mL screw-capped polypropylene centrifuge tube.
3. Matrix spikes and method blanks were prepared by spiking the serum (or water) with the analytes of interest;"In addition, l3C PFOA was added as a
; surrogate to all serum samples, calibration standards, matrix blanks, and method blanks at a concentration of 3.01 ng/mL to evaluate xtraction method performance
4. Two milliliters of acetonitrile were added to th serum and the centrifuge tubes were capped and vortex mixed, allowing the serum proteins to precipitate,
5. The tubes were centrifuged at approximately 3000 ref for 20 minutes to pellet the precipitate.
6. After removal from the centrifuge, the supernatant was transferred to an autovial for analysis.
Quantification was accomplished by high performance liquid chromatography tandem mass spectrometry. The following parameters were used:
Liquid Chrom atograph: Hewlett-Packard Series 1100 Liquid Chromatograph
system ;:'.' ,
, ---
Analytical column: Keystone BetasilTM Cjg 2x100mm, 5pm particle size
Column temperature: 30 C
Stop Time: 20.0 m inutes
Flow rate: 300 pL/min .
Injection volume: 5 pL
Mobile phase components:
Solvent A: 2.0 mM ammonium acetate in ASTM Type I water
Solvent B: HPLC Grade Methanol
'
Solvent Gradient:
~
Time 0.00 1.00 14.50 15.50 16.50 20.00
%B 20% 20% 90% 90% 20% 20%
Page 5 o f 18
G
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Mass Spectrometer: MDX Sciex API 4000, Q-Trap Mass Spectrometer Detector Software: AnalystTM Version 1.4 Ionization Mode: Electrospray Negative Temperature: 450 C GS1: 35 GS2: 45 Entrance Potential: 10 Analysis Type: Multiple Reaction Monitoring (MRM)
Table 5. Acquisition Parameters
PFBA (G, acid) NFPACs Acid PFHA (C6acid) TDHA (C7Acid) PFOA(CsAcid)
C9 Acid C10Acid Cn Acid C12Acid
FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS PFOA [1,2-13C]
P m M M itlfrC T i 213.0 262.9 313.0 362.9 413.0 463.0 512.9 563.0 613.0 297.9 497.9 298.9 398.9 498.9 426.9 526.9 414.9
168.9 219.0 268.7,118.9 318.7,168.8,118.9 368.9,219.0,169.0 418.7,268.9,218.9 468.8, 218.9,269.1 518.7,268.9,218.8 568.7,168.9,318.7 78.0 77.9 98.9,79.9 98.9,80.0 80.0, 99.2,130.0 406.8,80.9 506.7,81.0 369.8
-30 -30 -45 -35 -40 -50 -100 -45 -50 ` -55 -90 -65 -95 -80 -70 -70 -40
When multiple transitions were monitored, the total ion current (TIC) was used to quantify each analyte, thereby providing greater sensitivity than individual Q3 ion measurements.
4.1 Calibration ,4.1.1 Calibration Curve An extracted calibration curve was formed by spiking rabbit serum at prescribed levels and extracting the curve in the same manner as the samples. Stock solutions were individually prepared from neat fluorochemicals and diluted in methanol (except PFBA, which was prepared in Milli-Q water to prevent esterification from occurring). Samples were quantified versus an 8-point extracted calibration curve. The regression analysis was performed using a quadratic curve fit weighted 1/x.
Page 6 o f 18
7
3M ENVIRONMENTAL LABORATORY PROJECT NO. E05-0120
Calibration standards were within 20% (25% for the Lower Limit of Quantitation (LLOQ)) with a coefficient of determination >0.995. Low-level calibration standards, which were not within 25%, were not included in the calibration curve. Calibration standards that were not greater than twice the method blanks were not included in the calibration curve. 4.12 Continuing Calibration Verification (CCV) A Continuing Calibration Verification (CCV) was run at least once every 10 samples, bracketing the samples with the calibration curve. The CCV recovery was within 25% for all analytes. 4.13 System Suitability Five system suitability standards were analyzed before the initial calibration curve and after the last CCV. These samples had area counts with a %RSD o f <5% and a retention time %RSD of <2% when evaluated independently except for the following instances: Several individual transitions monitored for the Cio Acid failed the retention time system suitability criteria However, the data reported was derived from the quantitation o f the TIC, which passed system suitability requirements. All o f the system suitability sets for FBSA area counts,failed. The %RSDs were 6.2%, 7.5% and 8.4%. However, no samples had area counts above the LLOQ for this analyte therefore the data was accepted. 4.1.4 Lower Limit of Quantitation (LLOQ) The LLOQ for each analyte was equal, to the lowest standard in the calibration curve that met accuracy requirements o f 75% -125%. 4.15 Limit ofDetection (LOD) The LOD for each analyte was equal to the area counts (converted to a concentration) that w ere 2-3 tim es above the m ethod blank. 4.1.6 Blanks Method Blanks All o f the method blanks in this study had area counts < 50% o f the LLOQ. Matrix Blanks Two matrix blanks were prepared in rabbit serum and analyzed with the samples. One matrix blank contained endogenous levels of PFOS that were above the LLOQ. An average endogenous value for PFOS was determined by substituting a number equal to % the LLOQ for BLK050203-003.
% Page 7 o f 18
3M ENVIRONMENTAL LABORATORY PROJECT NQ.E05-0120
Table 6. Average Endogenous PFOS Value Determination
.f?1`Jr!"-!?*.. 4" . fesissss&w
PFOS
LLOQ (ng/mL)
0.306
Blk050203-003
< LLOQ
Blk050203-004
1 0.477
Average:
0.315
The average endogenous PFOS value was used to correct the matrix spike
response for endogenous levels of PFOS in rabbit serum.
4.1.7 Solvent Blanks
Acetonitrile blanks were analyzed throughout the analytical run. Analyte response was
less than lAthe LLOQ in all cases.
. 4.1.8 Surrogate.....
.....
13C PFOA was added as a surrogate to all serum samples,.calibration standards, matrix blanks, and method blanks at a cpncentration of 3.01ng/mL to evaluate the extraction method performance. All surrogate recoveries were within 20%.
4.2 Laboratory Control Spikes (LOS)
Six Laboratory Control Spikes (LCS) were prepared in rabbit serum and analyzed with the samples. Results were corrected for endogenous levels of analyte in the matrix (where appropriate), and are presented belowv ^
Table 7. Matrix Spike Recoveries in Rabbit Serum
PFBA (C4 acid) LOD =0.426 ng/mL
LLOQ 3.00 ng/mL
S am p lo ID
QC050203-001 QC050203-002 QC050203-003 QC050203-004 QC050203-005 QC050203-0QS
3.00 ........ 3.00 ' :
' 3.00 7 5 . 6 ....
..... 75.6 75.6
r ?>
< LLOQ .
"< LLOQ < LLOQ 70........
-..... 71.3
. . . 70 2
NA
NA
NA...
93% 94%
93%
. 881
NA
1.0%
NFPA (C5 acid) LOD 4.53 ng/mL LLOQ = 15.3 ng/mL
N A = N ot Applicable
QC050203-001 QC050203-002 QC050203-003 QC0502D3-004 QC050203-005 QC050203-006
3.06 3.06 3.06 77.7 77.7 77.7
< LLOQ < LLOQ < LLOQ 68.00
80.50 97.20
'
NA ' NA
NA 88% 104% 125%
NA 17.9%
Page 8 of 18
1
tiM HRipSTable 7. Matrix Spike Recoveries inRabbit Serum(continued)
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
PFHA (C6 acid) LLOQ = 1S.1 ng/mL
TDHA (C7 acid) LLOQ * 3.03 ng/mL
QC050203-001 QC050203-0Q2 QC050203-003 QC050203-004 QC050203-005 QC050203-006
3.03 3.03 3.03 76.8 76.8 76.8
LLOQ < LLOQ <UOQ
62.4 77.2 94.2
NA ...| NA .
v' : . NA ; 81% . 101% . 123%
NA 20.4%
QC050203-001 QC050203-002 QC050203-003 QC050203-004 QC050203-005 QC0502P3-OOS
:
3.03 3.03 3.03 , 76.5 76.5 76.5
< LLOQ < LLOQ < LLOQ
66.9 80.1 95.4
NA NA NA 87% , 105% 125%
NA 17.7%
C1ACID LLOQ *=3.12 ng/mL
QC050203-001 QC050203-002 QC050203-003 QC050203-004
QC050203-005 QC050203-006
3.12 3.12 3.12 -, 78.6 . 78.6 , 78.6
<LLOQ < LLOQ < LLOQ
65.4
71.9 83.1
NA NA NA 83%
91% ' ' 106%
NA 12%
^ ...........
C11 ACID LLOQ 0.297 ng/mL
- , ....- , ........................................................ 1 ... - ............................................ QC050203-001 * 2.97 2.98 100%
QGQ50203-Q02
2.97
2.71
91% :
. 5.1%
QC5Q2Q3-0P3 . ,2J97
2.95
99%
QC050203-004
75.3
. 75.8
101% :
QC050203-005 :..... 75.3.
78.3 : ..J 104%
1.8%
QC050203-006 .......75.3
...........78.2
104%
1
I .... " ... : ..........- y - . ......................................... .............................................. ,
QC050203001
3.00
3.04
' 101%
C12AC1D
; QC050203-002 ; QC050203-003
3.00 .......... 3.13 3 .0 0 .... ...... 3.28
: 104% 109%
LLOQ =0.747 ng/mL
QC05Q203-004- ...... 75.6...... ...... 76.2
QC050203-005
75.6
82.2
101% . - 109%
QC050203-006
75.6
78.3
104%
:V .:, 1
3.8%
3.9%
NA = N ot A pplicable
Page 9 of 18
I
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
------- :-- J.
f: J
Ariafyte *_-,**- arrt!&
WEBr? isr - m H K a w
n m ir^
*r
,j '
R . > W %
:' . .
QC050203-001
3 i;
2.81 93%
QC050203-002
' 3.01 . - -
3.06
102%
tsC PFOA
QC050203-003
3.01
QC050203-004 ...............3.01
2.94 2.68
98% 89%
4.8%
QC050203-005
3.01
2.91 97%
QG050203-006 . ... 3.01
2.75 :
.. 91%
..
C9 Acid LLOQ = 0.303 ng/mL
QC050202-001 .
... 3.03
QC050202-002 . ........ .. 3.03 .............
QCQ50202-003
3.03 '
QC050202-004
75.4
QC05202-005
75:4 :
QC050202-006
75.4
3.23 3.04 2.95 - ; -77.4. , 75.8 69.9
-
107% 100% 97% 103% 101% 93%
4.7% 5.3%
PFOA LLOQ 0.298 ng/mL
.
FBSA LLOQ = 0.303 ng/mL
FOSA LLOQ = 0.300 ng/mL
QC050202-001 QC050202-002 QC050202-003 QC050202-004 QC050202-005 QC050202-006
2.98 ....... 2.98 2.98 75.6 75.6 75.6
QC050203-001
QC050203-002 QC050203-003 QC050203-004 QC050203-005
QC050203-006 ............
3.03 3.03 3.03 78.5 .... 76.5 ............... 76.5
QC050203-001 QC050203-002 QC050203-003
QC050203-004 QC050203-005 QC050203-00
3.00 3.00 3.00
75.9 75.9 75.9
2.93 2.58 2.65 75.2 r 76.4 ' 77.6
2.96 2.92 2.95 75.9 77.9 77.7
2.78 2.74 2.74 76.6 " 77.1 ' 76.0
98% 87% 89% 99% 101% 103%
98% 96% 97% 99% 102% 102%
93% 91% 91% 101% 102% 100%
6.8% 1.6%
0.7% 1.4%
0.8% 0.7%
Page 10 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.EQ5-0120
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
ij s is k ;
PFBS LLOQ = 0.303 ng/mL
PFHS LLOQ - 0.315 ng/mL
QC0502C3-^ QC050203-002 QC050203-003 QC05203-004 QC050203-05' QC050203-006 '
--
: c,, 3.06 : 1 ^ 0
3.03T ....... -
3.00
99%
.........3.03
3.01 99%
76.8 :
75.8 99%
. ! 76.8 ""
78.3 102%
76.8 .........
77.2 '
101%
- ' ` -r....... " *
QC0502C3-001..... ..........3.15
QC0502S03-02 ....... 3.15
QC050203-003
3.15
QC050203-004
79.8
QC050203-005
79.8
QC050203-006
79 8
3.04 . ...... 3.08
3.04 78.2
79.9 78,6
V 97% . 98% 97% 98% 100% 98%
I
1.1% 1.6%
0.8% 1.1%
THPFOS LLOQ =0.780 ng/mL
QC05203-001 QC050203-002 QC050203-003 QC050203-004 QC050203-005 QC050203-006
. 3.12 3.12
... 3.12 78.9 78.9
r ' . 78.9 : .
3.02 2.83 ' 2.83 . 66.0 80.0 96.5
97% 91% 91% ! . 84% 101% 122%
3.8% 19%
I QC050203r001
THPFDS
... QC050203-002 ....QC050203-003 ...
LLOQ - 0.303 ng/mL ..... QC050203-004 .. QC050203-005
QC050203-906
. 3.03 ........
2.96
3.03 ____ - J .;3:oov:
98% ' 99%
.
. 3.03 - ..... . 3.12 ' ' 103%
76.5' ........ . .... 77.9
76.5
79.8
102% 104%
76.5 ;
78.2 102%
2.8% 1.3%
Page 11 o f 18
it
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 8. PFOS Matrix Spike Recovery in Rabbit Serum, Corrected for Endogenous Levels
; LLOQ=G.303 nn/mL
QC0^2D2-Ooi QC050202-0Q2 QC05Q202-003 QC50202-004 QC05D202-005 QC050202-006
3^6 3.06 3.06 77.4 77.4 77.4
-- ----------------
it V V : 1`-m tiserved ^ rj
Eijaoflnous 'Level in Jllatrix.
7lUe;fcoveiy,, '
:
I -` -ng/mL'
E n d lje iffiU s -
U ve i. nn/mL
3.17 V 0.315
2.86 ^ 93%"^ ' " ^
3.03 . 0.315 .
2.72
89% 2.5%
3.1
0.315 .
2.79
91%
77.4 . 0.315 . .
77.1
100%
77.6 0.315
77.3
100%
1.1%
76.1 0.315
75.8 98%
4.3 Accuracy The accuracy for each analyte reported was calculated by taking the average of the matrix spike recoveries for that analyte. The results are presented below.
Table 9. Method Accuracy for individual Analytes
l- "`u --
-,
% Accuracy
Analyte , '% ,Accuracy:
PFBA*
7%
C12 Acid
5%
NFPA*
6%
FBSA
1%
PFHA*
2%'
FOSA
4%
C7 Acid*
6%
PFBS
1%
PFOA
' 4%
PFHS
2%
C9 Acid
1%
PFOS
5%
C10 Acid*
7%
THPFOS
2%
C11 Acid
1%
THPFDS
1%
The %Accuracyreported for this analyte is based on the high concentration spike recovery data only because the low concentration spike recoveries were less than the LLOQ.
4.4 Sample Related Comments
The extraction and analysis of the samples was performed utilizing a non-validated method. The matrix spike results, 13C PFOA surrogate recoveries, and the extrapolated calibration curve (between the LLOQ and LOD) should be considered when evaluating the accuracy and precision of the sample results.
ilSKBi
Tables 10 and 11 summarize individual sample data.
Page 12 o f 18
15
Table 10. Perfluorinated Acid Results
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
TNA 6840 TNA 6843 . TNA6847 TNA 6934 TNA 6935 TNA 6944 TNA 6959 TNA 6960 TNA 6967 TNA. 6973 TNA 6975
Wtvi.*-.JSSySn
:5.19 0.990* 0.507* <LOD 1.17* ; 7.08 4.91 3.32 4:09 6.73 2.95*
* 2.50 cLOD LOD <LOD <LOD cLOD <LOD cLOD CLOD 3.56 CLOD
f(|
j v - t f| - >i t i
'-S i m & m IS illi h
" CLOD ; . CLOD
CLOD
CLOD CLOD CLOD " CLOD clod; CLOD CLOD CLOD
CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD 0.888* CLOD
5.48 0.581 4.61 7.69 5.19 7.38 3.13 4.59 5.30 5.51 5.52
1.52 0.574 0.975 2.26 1.63 1.45 2.45 1.11 1.62 1.64 1.31
mm w '.
' : -is,!
CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD
CLOD CLOD CLOD CLOD 0.451 CLOD 0.700 CLOD CLOD CLOD CLOD
CLOD cLOD CLOD cLOD CLOD cLOD CLOD cLOD cLOD CLOD CLOD
! Page 13 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 10. Perfluorinated AcicJ Results (continued)
Sarnpi^ D
PFHA | T D H A -
(n g/in U (ng/m L) (ng/m L )i(ng/m l.)
jS&ET
G12 A bipr
(ng/m L ) `(rglmU-
I LLQ iing/m UK :
3.00
- 1r , 15.3 1 5 :1 1 } 3.030
LOD
a - " j , . , J
r~0 .4 2 6 2 .3 4
1 5 3 j 0.725 / J
TNA 6977" 5,04
CLOD CLOD cLOD
~~ ~ 1C ______
I p->
0.477 CLOD
3.12 I CLOD '
0.297 ' --
'01Si7i14-v7>ril<*
cLOD
cLD
TNA 6981 6.76
2.45 <LOD CLOD 4.12
T.28 CLOD
cLD ' CLD
TNA 6992 0.690* <LOD cLOD cLOD 4.76 0.912 . cLOD
CLOD
cLOD
TNA 6994 CLOD ' CLOD cLOD cLOD 1.15 0.337
TNA 6995 1.98* CLOD
1.02* 3.58 2.63
CLOD CLOD
CLOD 0.815
CLOD cLOD
I:
'CVO;
TNA 6997 3.90
CLOD CLOD cLOD
3:46
2.52
cLOD
0.842
<LOD
TNA 7000 3.34
cLOD CLOD CLOD
23.0/
1:08
cLOD
cLOD
cLOD
TN 7006 3.19
CLOD CLOD cLOD :4.18
1.09
CLOD
cLOD
CLOD
TNA 6938 <LOD <LOD. cLOD CLOD 5.00 0.979
cLOD
CLOD
cLOD
TNA 6939 CLOD CLOD . , CLOD cLOD 2.32 0.941
CLOD
0.312
cLOD
, TNA 6941 3.56 cLOD CLOD CLOD : 5.82
1.69
<LOD,,
0.620
cLOD
TNA 6950 <LOD CLOD cLOD CLOD : 3.87
0.723
14.0***
cLOD
CLOD
TNA 6953 0.621* <LOD CLOD cLOD " 5.49
0,725
CLOD
cLOD
cLOD
TNA 6955 <LOD cLOD cLOD cLOD
2.54
0.562
CLOD
CLOD
CLOD
TNA 6952 cLOD cLOD CLOD cLOD 4.68 0.941
CLOD
CLOD
cLOD
TNA 6964 <LOD , <LOD CLOD CLOD; 5.61 1.58 cLOD
CLOD
CLOD
TNA 6956 TNA 6970
<LOD CLOD <LOD . cLOD
cLOD cLOD
cLOD cLOD
4.73
6.00
1,35 1.42
cLOD CLOD
cLOD : CLOD
CLOD
cLOD
TNA 6972 <LOD CLOD CLOD . cLOD
3.40
1.09
CLOD
CLOD / CLOD
TNA 6978" <LOO CLOD CLOD CLOD cLOD <LOD
CLOD
cLOD
CLOD
TNA 6979 <LOD CLOD <LOD CLOD 3,32
0.981
cLOD
<LOD
cLOD
TNA 6982 <LOD <LOD CLOD cLOD 1.48 0.664
CLOD
cLOD
cLOD
TNA 6984 <LOD TNA 6986 0.530*
CLOD CLOD
CLOD <LOD
CLOD cLOD
2.84 2.08
0.955 0.645
CLOD CLOD
<LOD CLOD :
cLOD CLOD
TNA 6988 ' CLOD CLOD CLOD CLOD 2.57
0.881
CLOD
CLOD
cLOD
Mean Median
High Low
3.33 3.33 7.08 0.507*
2.84 2.50 3.56 2.45
NA ... : 0^954*.
NA 0.954*
NA 1;02* NA 0.888*
.4.61 ; 4.59
23.0 0.477
1.25 1.09 2.63 0.337
NA NA NA NA
0.623 0.660 0:842 Q.3T2 - `
NA NA NA NA
Standard Deviation
#OF HITS
2.17
20
0.627 3
NA 0.0933 . 3.64 0.571
0 2 35 34
NA
0
0;208
NA
6 ' : ......0
NA = Not Applicable Analyte concentration was below the LLOQand above the UOD. TN-A-6977 and TN-A-6978 are fromthe same lot ofpooled serum. Analyte was detected in one o f the 36 samples but appears to be a contaminant or an anomaly; the
sample w ill be reanalyzed and the results w ill be reported in the definitive study. Based on !3C PFOAsurrogaterecovery, the overall method uncertainty is +/- 20%.
!r Page 14 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 11. Sample Results for Additional Perfluorinated and Highly Fluorinated Analytes
TNA 6840 TNA6643 TNA 6847 TNA 6934 TNA 6935 TNA 6944 TNA 6959 TNA 6960 TNA 6967 TNA 6973 TNA 6975 TNA 6977" TNA 6981 TNA 6992 TNA 6994 TNA 6995 TNA 6997 TNA 7000 TNA 7006 TNA 6938 TNA 6939 TNA 6941 TNA 6950 TNA 6953 TNA 6955 TNA 6962 TNA 6964 TNA 6966 TNA6970 TNA.6972 TNA 6978** TNA 6979 TNA 6982 TNA 6984 TNA6986
<LOD <LOD <LOD cLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD cLOD CLOD CLOD cLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD CLOD cLOD CLOD CLOD
<LOD <LOD 0.0458* CLOD CLOD CLOD CLOD CLOD 0.199* CLOD CLOD cLOD 0.0311* CLOD cLOD CLOD CLOD CLOD cLOD CLOD cLOD CLOD CLOD CLOD CLOD <LOD CLOD
CLOD
cLOD CLOD cLOD 0.0344* cLOD CLOD cLOD
cLOD 0.0228* ctOD 0.0304* 0.0433* 0;Q706* <LOD 0.0292* 0;0358* CLOD Q.0393* 033339* 0.0313* 0.0429* LOD 0.0366* 0.0479* 010568* 0.0412* 0.0226* cLOD 0.0224* CLOD 00226* CLOD 0.0312* 0.0374* 0.0229* cLOD 0.0345* 0 .0210* 0.0228* cLOD cLOD CLOD
4.39 0.780 ' 2.05 2.41 2.14 4.73 3.75 4.52 4.27 5.18 4.98 ; 0.844 1.77 4.45 1.71 3.79 3.81 5.68 4.90 2.78 1.79 3.06 3.24 5.24 3.29 ' 5.22 5.80 4.62 4.06 3.09 0.945 2.31 -1.26 1.73 1.41
23.0 3.42 23.7 32.8 16.2 20.4 1.4.8 19.6 21.3 20.5 19.4 3.01 17.4 19.8 3.50 15.1 15.2 22.9 20.2 15.6 6.23 23.4 14.3 22.1 10.1 19.8 21.7 17.5 17.0 12.7 2.71 16.7 9.37 15.8 11.3
<LOD <LOD cLOD cLOD cLOD CLOD cLOD CLOD CLOD cLOD. CLOD cLOD CLOD cLOD CLOD cLOD CLOD cLOD CLOD CLOD cLOD <LOD cLOD CLOD cLOD CLOD cLOD CLOD CLOD cLOD cLOD cLOD cLOD cLOD CLOD
0.124* 0.155* 0.145* 0.0531* 0.0820* 0.0860* 0.0649* 0.0819* 0.0857* 0.0818* 0.0622* 0.0916* 0.103* 0.0826* 0.0616* 0.08531 0.0707* 0.0638* 0.0667* 0.061* 0.0625* 0.0577* 0.099* 0.0480* 0.0493* 0.0705* 0.101* 0.0620* 0.137* 0.0653* 0.0998* 0.102* 0.0790* 0.0911* 0.0683*
Page 15 o f 18
\C
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 11. Sample Results for Additional Ferfluormatedand Highly Fiuorinated Analytes (continued)
`F. ^g
1 Sam ple ID f ,5 B,S*
is *
r f fflfttiL ) iflg/mfcV
* It f v
i-L O Q (ng/m L) 0.303 t *':! K*-r
Mn
0.0268 :S s ffb lD 2 6 i
' TNA 6988 r
<LOD <LOD <LOD
1.79
Mean
NA 0.0776* 0.0348* 3.27
. Median
NA 0.0401* 0.0339*: 3.27
High
NA 0.199* 0.0706* , 5.80
Low NA 0.0311* 0.0210* 0.780
gf " lib i
16.5 16.3 1.9 32.8 2.71
ap& g,7B b "i ' 0;3'a-aS"StJ
<LOD NA NA NA NA
0.0979* 0.0839* 0.0819* 0.155' 0.048*
Standard Deviation NA
0.0812 0.0122
1.52
6.71
NA .0257
# OF HITS
0 4 .. 23 36 36
NA = Not Applicable
.
...
Analyte concentrationwas below the LLOQand above the LOD.
TN-A-6977 and-6978 are from the same lot of pooled serum.
Based on I3C PFOA surrogaterecovery, the overall method uncertaintyis +/- 20%.
0
36
Table 12. Isomer Ratios for Individual Samples
TNA 6840 TNA6843 TNA 6847 TNA 6934 .... TNA 6935 TNA 6944 TNA 6959 TNA 6960 TNA 6967 TNA 6973 TNA 6975 TNA 6977** TNA 6981 TNA 6992 TNA 6994 TNA 6995 TNA 6997 TNA 7000 TNA 7006 TNA 6938 TNA 6939 TNA 6941
pH . ?
tS2
"-P F Q S r S fe .
* J j S] SampIflrGngn
-'Branched Branched
S S l 8 # M a S a M i l `l , 7SftTTor'^r
California .
11%
40%
Missouri
13% 40%
Pennsylvania Pennsylvania
New York
4.1%
0.8% 12%
43%' 45% 37%
Michigan,
3.4%
35%,
Virginia
4.3%
40%
Virginia
4.5%
38%
Maryland
" 9.5%
43%
Montreal, Qubec
' 4.3% :> 42% Vi..:.
Montreal, Quebec
4.0% ,
42%
Massachusetts........... < LLOQ*
39%
Texas
3.7%
43% '
California
4.2%
40%
California
4.0%
39%
California
6.0%
41%,
California
4.0%
41%
California
17% 41%
California
6.3%
41%
New York
2.7%
44%
New York
4.0%
35%
New York
3.0%
36%
Page 16 of 18
n
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 12. Isomer Ratios for Individual Samples (continued)
TNA 6950 V TNA 6953
TNA6955 TNA 6962 TN6964 TNA 6966 TNA 6970 TNA 6972 TNA 6978" TNA 6979 TNA 6982 TNA 6984 TNA 6986 TNA 6988
"Michigan Michigan Michigan Virginia Virginia Virginia
. Maryland Maryland
Massachusetts Massachusetts
Texas Texas Texas Texas
0.3%
10%
3.0%
6.8%
5.4% 7.9% 6.7% 5.1% < LLOQ* 7.6%
6.0%
1.3%
0.1%
4.5%
1vlAHHm5sra^3
39% 39% 35% 41% 42% 40% 39% 38% 41% 30% 41% 31% 43% 33%
Average:
Standard Deviation Sam ple value w as < LLOQ T N -A -6977 and TN -A -6978 are from the same lot o f pooled serum.
6%
3%
39% 3%
All original raw data and the analytical report have been archived at the 3M Environmental Laboratory. The test materials and analytical reference-standard reserve samples, as well as the samples pertaining to this project are archived at the 3M Environm ental Laboratory.
Reserve samples, digital copis o f original (lata and all original paper data will be retained in the archives o f 3M Environmental Laboratory for a period of at least 10 years following report signing.
Under the conditions of the study, endogenous fluorochemicais were found to be present in all samples. PFHS, PFOS, and THPFDS were detected in every lot of serum while PFOA was present in detectable levels in all but one sample. Conversely, FBSA, THPFOS, and the C12 acid were not detected in any o f the samples using the present methodology. 13C PFOA surrogate recoveries were all within =20%.
Page 17 o f 18
is
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
William Reagen, Laboratory Manager
Date
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
QualityAssurance Representative
Date
Page 18 o f 18
AAUG. 12, 2 O 05 5 ; ' 1 PM jQUALITY ASSOCIATES K U1
NO. 074J P. 1/'
3WENmONUSNTAL LABCRATORY PROJBCTNO.S0S-012D
report for tbis projecL
RECEIVED TIME AU5.12. 4;48PM
P a e e lS o flS
PRINT TIME A6, 12. 4:49PM lo
